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Issue 19, 2014
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Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80 and Ho2MN@C80 families (M = Sc, Lu, Y)

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Abstract

The paramagnetic NMR study of HoM2N@C80-Ih and Ho2MN@C80-Ih nitride cluster fullerenes (M = Sc, Lu, Y) reveals strong dependence of Ho-induced paramagnetic shifts (δpara) in 13C NMR spectra on the size of the diamagnetic metal in the cluster. In particular, the δpara value in HoY2N@C80 is almost doubled in comparison to that in HoSc2N@C80. X-ray magnetic circular dichroism studies show that all Ho–nitride cluster fullerenes have the same magnetic ground state of Ho3+. Point-charge ligand-field splitting calculations show that the increase of the M3+ radius in going from Sc to Y results in a considerable increase of the energy splitting between different Jz states. This leads to a 19% higher magnetic anisotropy of Ho3+ in HoY2N@C80 than in HoSc2N@C80 at 300 K. Variations of the molecular geometry and cluster dynamics with the size of the cluster are found to have even greater influence on δpara values. This work shows that the magnetic properties of the species confined inside the fullerene cages can be tuned using the geometrical factors such as the cluster and the cage size.

Graphical abstract: Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80 and Ho2MN@C80 families (M = Sc, Lu, Y)

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Publication details

The article was received on 27 May 2014, accepted on 25 Jul 2014 and first published on 05 Aug 2014


Article type: Paper
DOI: 10.1039/C4NR02864C
Citation: Nanoscale, 2014,6, 11431-11438
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    Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80 and Ho2MN@C80 families (M = Sc, Lu, Y)

    Y. Zhang, D. Krylov, S. Schiemenz, M. Rosenkranz, R. Westerström, J. Dreiser, T. Greber, B. Büchner and A. A. Popov, Nanoscale, 2014, 6, 11431
    DOI: 10.1039/C4NR02864C

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